Baeyer-Villiger oxidation reaction is an important reaction to oxidize a cyclic ketone or a linear ketone into a more complicated and valuable linear ester or lactone. As an important polyester monomer, ε-caprolactone is mainly used to synthesize poly ε-caprolactone, and can be copolymerized or blended with various resins to improve the gloss, transparency and anti-adhesion of products. With the enhancement of people's awareness on environmental protection, it is also expected to replace the current common plastics to launch into the market of disposable packaging materials and plastic films in quantity, and has a broad prospect. In view of the factors such as raw materials, equipment and reaction conditions, a cyclohexanone oxidation method is the most effective method and is also the current method for industrial production of ε-caprolactone (Chemical Reagent, 2003, 25(6):363-364).
According to different oxidants used in the reaction, the cyclohexanone oxidation method can be divided into four methods: a peroxyacid oxidation method, a H2O2 oxidation method, a biological oxidation method and a molecular oxygen oxidation method. As an oxidant, molecular oxygen is an ideal oxidant for cyclohexanone oxidation since it overcomes the disadvantages of other three oxidation methods such as high risk, low yield and high cost, and has the advantages of safety, low cost, less by-products and less environmental pollution. However, due to the weak oxidizing ability of the molecular oxygen, direct oxidation of cyclohexanone with the molecular oxygen cannot achieve satisfactory results, and aldehyde co-oxidants and appropriate catalyst are usually added to oxidize cyclohexanone in the reaction process. Patent CN102408404A reports a method for preparing ε-caprolactone by oxidizing cyclohexanone through molecular oxygen. Although a catalyst is avoided in the reaction process, there are also potential safety hazards since azobisisobutyronitrile is used as an initiator. Moreover, using benzaldehyde as a co-oxidant causes difficulties for subsequent separation and purification, and increases the industrial cost. Patent CN102391238B uses a metalloporphyrin compound to catalyze cyclohexanone and the molecular oxygen to prepare ε-caprolactone by oxidation, which has high selectivity and a small amount of adjuvants, but a homogeneous catalyst is difficult to separate and expensive. Patents CN105440005A and CN 105440006A respectively propose methods for preparing ε-caprolactone by using magnesia-alumina hydrotalcite and MgO/Fe2O3 catalyst to catalyze and oxidize cyclohexanone, wherein molecular oxygen is used as an oxidant, and a solid catalyst is easy to recover. A non-metal carbon material has the characteristics of good stability and high catalytic activity. It is found by Nabae (ACS Catalysis, 2013, 3:230-236) et al. that Ketjen carbon black has good catalytic activity for the reaction of synthesizing the ε-caprolactone by oxidizing cyclohexanone, wherein a conversion of the cyclohexanone reaches 61%, and a yield of the ε-caprolactone reaches 61%. It is found by Li Yuefang (Carbon, 2013, 55:269-275) et al. that, at a room temperature, a conversion of ε-caprolactone, synthesized by oxidizing cyclohexanone catalyzed by graphite, is as high as 92.5%, and the selectivity of ε-caprolactone is 100%. Patent CN103274883A also discloses a method for catalyzing and oxidizing cyclohexanone to synthesize ε-caprolactone by using a carbon nanotube as a catalyst.
Aldehydes are mainly used as co-oxidants in the cyclohexanone molecular oxygen oxidation method, and the commonly used aldehyde co-oxidants comprise acetaldehyde, propionaldehyde, isobutyraldehyde, isovaleraldehyde, benzaldehyde, p-tolualdehyde and so on. Usually, benzaldehyde or p-tolualdehyde is the preferred co-oxidant (CN105440005A; CN105440006A; CN103274883A; CN102408404A; CN102391238B). However, a lower benzaldehyde efficiency (yield of ε-caprolactone/conversion of benzaldehyde) limits the economic feasibility of the cyclohexanone oxidation using molecular oxygen as oxidant. For example, the highest efficiency of the benzaldehyde reported by Nabae (ACS Catalysis, 2013, 3:230-236) et al. is 0.77. Moreover, the benzaldehyde is converted into benzoic acid in the reaction process, and the value thereof is reduced. Therefore, on the basis of satisfying the reaction stoichiometry between cyclohexanone and co-oxidant, to develop a co-oxidant with low molecular weight and high efficiency is of great significance to improve the economy of the process. Acrolein and acrylic acid are both value-added chemical intermediates in the chemical industry. Up to now, there have been no reports on the use of acrolein as co-oxidant for Baeyer-Villiger oxidation of cyclohexanone.